Textile finishing



Patented Dec. 30, 1941 UNITED STATES PATENT OFFICE TEXTILE FINISHINGtion of New York No Drawing. Application May 27, 1939, Serial No.278,122

'7 Claims.

The invention relates to textile finishing, and in particular tocompositions and a treatment for improving the softness, pliability,draping qualities, and other characteristics of textile fibers, yarns,threads and fabrics. It is especially concerned with means for improvingthe quality of fabrics composed entirely or in large part of celluloseor cellulose derivatives.

The improvement of textile materials by treatment with substances knownas softening or finishing agents is not a new expedient, but it had"assumed additional importance with the intro= duction and increasing usein the textile art of artificial oellulosic fibers. By permeating orimpregnating cellulosic fabrics, yarns, threads and the like with verysmall quantities or a suitable finishing material, it has been foundpossible to improve substantially the softness, pliability and otherqualities oi such products, which enhances their appearance, hand andgeneral attractiveness to the consumer. Substances heretofore proposedin the art for such finishing treatment have not been entirelysatisfactory. In many cases they have been only partially et fective intheir softening action, and, through inability to be completely andfirmly adsorbed by the fiber, generally have lacked permanency andresistance to extraction by washing or other cleaning operations. ()therobjections in pre vious finishing agents include their required use inlarge and expensive quantities, the tendency to impart a greasy orotherwise undesirable surface on the fiber, or, in the case of somesub-= stances, interference with the dyeing properties of the textile.

It is an object of the present invention to provide improved textilefinishing compositions, which are largely free from the above-mentioneddisadvantages, and which are capable in a fiber or fabric treatingprocess of effecting a more permanent and satisfactory softening action.A further object is to produce in cellulosic fabrics, yarns, threads,and like products, an improved fullness, softness, pliability and hand,which enhances the general adaptability and use of such products in thetextile art.

The above objects are accomplished through the use as finishing orsoftening agents of a group of organic compounds consisting ofglyoxalidines and certain of their derivatives.

These substances in very dilute aqueous solutions are capable ofimparting an excellent, and relatively permanent softening efiect ontextile materials. Glyoxalidines may be regarded as dehydration productsof certain amides, and they may be obtained by reacting polyamines andthe higher carboxylic acids under certain conditions. The manner offorming the compounds forms no part of the present invention, but theirpreparation can be represented by the following scheme:

0 l R.-OH+H:N.CH.CH.NH.R:.X H:O l 1 R1 R1 Fatty acid alkylenc polyamineAmide wherein R is an aliphatic group containing from it to 20 carbonatoms representing the residue of a higher fatty acid; R1 representshydrogen or a lower alkyl group; Ra represents an alkylene group or alower alkyl substituted alkylene group; and X represents a hydroxylgroup, an amino group or an amino-alkylene substituted imino group.

Within the scope of the present invention there are included asoperative compounds any of those falling within the above ring formula,which may be broadly termed 1,2-disubstituted glyoxalidines, and inwhich substitution also may be made in one or both of the 4 and 5positions. To promote solubility, or create desired pH effects, salts ofthese glyoxalidines may be used, in place of the free bases, inpreparing the treating bath, or the compounds may be dissolved in thepresence of acids. Quaternary ammonium salt derivatives can be preparedby reaction with an organic ester, and acids will react to form additionproducts. Since some glyoxalidines within the above formula may possessmore than one basic group, the particular nitrogen group neutralized bythe addition of, say, one mole of acid, cannot be indicated by a generalspecific structure, but for the purpose of the present invention, the(acid addition) products, as well as the quaternary salt derivatives,may be considered to include compounds of the following generalstructure:

in which R, R1, R2 and X are as indicated in the above formula; Yrepresents an'organic or inorganic acid radical, and R: is hydrogen, oran alkyl or aralkyl group. Reaction products with either acids orinorganic esters are intended to be included within the broad referenceherein to salt derivatives of the glyoxalidines, and suitablesalt-forming substances are acids such as formic, acetic, andhydrochloric acids, or inorganic esters represented by the compoundsdimethyl sulfate, diethyl sulfate, methyl iodide, and benzyl chloride.

Typical specific compounds within the above formulae which have shown anexcellent softening and finishing action are:

Example 1 HOCIHA- H:

l-hydroxyethyl-zheptadecyl glyoxalidine l-hydroxyethyl-2-heptadecylglyoxalidin was prepared by reacting 424 grams of hydroxyethyl ethylenediamine with 568 grams of stearic acid, in the presence of 400 cc. ofxylene. The mixture was refluxed and water continuously removed from thecondensate. In 12 hours 60 grams of water were thus collected and thetemperature reached 187 C. at the completion of the reaction. The xylenewas distilled off at 25 mm. pressure, and the excess hydroxyethylethylene diamine recovered by distillation to 200 C. at mm. pressure. Aportion of the l-hydroxyethyl-2-heptadecyl glyoxalidine thus formed wasconverted to the acetate by melting 350 grains of the compound with 60grams of glacial acetic acid. and another portion of :350 grams wasreacted with 154 grams of diethyl sulfate at 100 C. to form the compoundl-hydroxyethyl-lethyl-Z-heptadecyl glyoxahdonium ethylsulfate.

aaoasve These glyoxalidine compounds may be represented by the followingformulae:

nHu-C CH:

HOC:H4-N- H:

H 0.00pm

l-hydroxyethyl-Z-heptadecyl glyoxalidonlum acetate Calla-=0 CH:

HOCzHr-N Hz 7 l-hydroxyethyl-l-ethyl-2-heptadecyl glyoxalidonium ethylsulfate Aqueous solutions of these compounds were made with aconcentration of 0.25% of the finishing agent, and with adjustments to apH value of both 4.5 and 6.5. Pieces of rayon fabric, previouslyscoured, were immersed in these solutions for 5 minutes, with thetemperature of the bath at C. They were then removed, passed throughsqueeze rolls and dried on a mangle. The treated samples were evaluatedin point of hand" or softness, and in each of them the improvements inthe pliability, draping qualities, and softness were readily apparent.The solutions having a pH value of 6.5 exerted a slightly greatersoftening action than those of higher acidity, but an improved textilequality was imparted by each treatment.

Example 2 /N\ oi1nuo on,

HsNC:H4N H1 l-aminoethyl-Z-heptadecyl glyoxalldlne CnHu-C CH:

H:NC:H|N H: l-aminoethyl-Z-heptadecenyl glyoxalldine Following reactionconditions substantially similar to those of Example 1, the compounds 1-aminoethyl-Z-heptadecyl glyoxalidine and 1- aminoethyl-Lheptadecenylglyoxalidine were prepared by reacting diethylene triamlne with stearicacid and oleic acid, respectively. Addition products of theseglyoxalidines were readily formed by further reaction with acids oralkyl salts such as dimethyl sulfate, and in this mannor the followingderivatives were prepared:

Water solutions of each of these compounds, in a concentration of 0.50%,were made, and skelns of jute yarn were immersed in the solutions for aperiod of minutes, at a solution temperature of 80 C. The skeins werethen passed through a squeeze roll and air-dried. A definite softeningaction and improvement. in pliability was readily detectable in theyamlsample treated by each solution, although the finishing action ofthe stearic acid derivatives was slightly better than that of theothers.

Example 3 A series of compositions was prepared, including some of thecompounds illustrated in the two above examples, and others within thegeneral class 'of the described aminoethyl and hydroxyethyl heptadecylglyoxalidines. Samples of rayon, cellulose acetate, cotton and jutefabrics were treated by soaking in 0.5% aqueous solutions of thesecompounds, acidified with acetic acid to a pH of 6. The temperature ofeach solution was 60 to 70 C. and the immersion period was 6 minutes.After wringing and drying the samples, they exhibited a noticeablesoftening effect in all instances, which was particularly evident in thecellulose acetate and jute fabrics. The pH value of the soakingsolutions was found to be reduced to 5.7 to 5.8, suggesting theselective removal of the glyoxalidine from the solutions.

As will appear from the above examples, these new. finishing agents arereadily adsorbed by textile fibers, and are effective in concentrationsfrom about 0.1% to 1.0% by weight in a water solution or dispersion.Minute quantities of the glyoxalidine compound permeat the textilewithout leaving a greasy or other extraneous feel. and their resistanceto hydrolysis or removal by washing creates a substantially permanentsoftening efiect. In addition to producing a softer and more pliablefiber or fabric, these finishing agents render the material moresubstantive to direct dyes, or, where dyeing is effected before thefinishing treatment, they improve the fastness of the dye to washing.Water solutions varying over a wide range of acidity or alkalinity maybe used, and the proper functioning of the glyoxalidine derivatives isnot affected by hard water or the presence of lime salts. A preferredapplication of the invention is in the treatment of textiles composedentirely, or in large part, of cellulose or cellulose derivatives.Cotton goods are remarkably improved by these new finishing agents, andrough materials, such as denim, show a novel draping quality andsoftness after treatment. A most important present use of the inventionis in the treatment of rayon textiles, whereby a transformation intexture is effected more nearly resembling that of natural silk. Asimilar action is shown on unsized paper and wood-fiber goods.

"Many glyoxalidine derivatives other than those specifically describedare of contemplated use for the purpose of the invention, and variousalkylene polyamines may serve as the starting material in thepreparation of these compounds. These include diethylene triamine,triethylene tetramine, hydroxyethyl ethylene diamine, dipropylenetriamine and tripropylene tetramine. The hydroxyalkyl glyoxalidinederivatives have shown an especially effective textile softening action.The acids used in the glyoxalidine preparation may include generally thesaturated or unsaturated fatty acids having 12 or more carbon atoms, andcomprising lauric, palmitic, oleic, linoleic, ricinoleic, and stearicacids. Numerous modifications with respect to the operative and suitablecompounds are within the scope of the invention as defined by theappended claims.

The glyoxalidine compounds themselves and their method of preparation,are claimed in the copending applications of A. L. Wilson, Serial Nos.191,191 and 285,081, filed February 18, 1938 and July 18, 1939respectively.

We claim:

1. Process of finishing and softening textile materials which comprisesapplying to said materials a compound of the group consisting ofsubstances of the formula N R-C CH.R1 XR2l I--( 3H.R1

(wherein R is an aliphatic group containing from 10 to 20 carbon atomsrepresenting the residue of a higher fatty acid; R1 is one of the groupconsisting of hydrogen and lower alkyl radicals; R2 is one of the groupconsisting of alkylene and lower alkyl substituted alkylene radicals;and X is one of the group consisting of hydroxyl, amino andamino-alkylene substituted imino radicals); and salt derivatives ofthese substances.

2. Process of finishing and softening cellulosic fibrous materials,which comprises applying to said materials and adsorbing thereon afinishing agent composed of a compound of the group consisting ofsubstances of the formula GH.R1

H.Ri

, (wherein R. is an aliphatic group containing from X is one of thegroup consisting of hydroxyl,

amino and amino-alkylene substituted imino radicals); and saltderivatives of these substances.

3. Process of finishing and softening cellulosic fibrous materials,which comprises applying to said materials and adsorbing thereon afinishing agent, by immersion in an aqueous solution containing about0.1% to 1.0% of a compound of the formula R-C/ crmn X-RgN- H-R wherein Ris an aliphatic group containing from 10 to 20 carbon atoms representingthe residue of a higher fatty acid; R1 is one of the group consisting ofhydrogen and lower alkyl radicals; R2 is one of the group consisting ofalkylene and lower alkyl substituted alkylene radicals; and X representsa hydroxyl radical.

4. Process of finishing and softening cellulosic fibrous materials,which comprises applying to said materials and adsorbing thereon afinishing agent, by immersion in an aqueous solution containing about0.1% to 1.0% of a compound of the formula wherein R is an aliphaticgroup containing from 10 to 20 carbon atoms representing the residue ofa higher fatty acid; R1 is one of the group consisting of hydrogen andlower allwl radicals; R2 is one of the group consisting of alkylene andlower alkyl substituted alkyiene' radicals; R3 is one of the groupconsisting of alkyl and aralkyl radicals; X is one of the groupconsisting of hydroxyl, amino and amino-alkylene substituted iminoradicals; and Y is one of the group consisting of fatty acid, alkylsulfate and inorganic acid radicals.

5. A soft, pliable textile material composed of or containing cellulosicfibers having intimately associated therewith and strongly adsorbedtherein a finishing agent composed of a. compound of the groupconsisting of substances of the formula (wherein R is an aliphatic groupcontaining from 10 to 20 carbon atoms representing the residue of ahigher fatty acid; R1 is one of the group consisting of hydrogen andlower alkyl radicals; R: is one of the group consisting of alkylene andlower alkyl substituted alkylene radicals; and X is one of the groupconsisting of hydroxyl, amino and amino-alkylene substituted iminoradicals) and salt derivatives of these substances.

6. A soft, pliable textile material composed of or containing cellulosicfibers having intimately associated therewith and strongly adsorbedtherein a finishing agent composed of a compound of the group consistingof substances of the formula /N\ R(IJ/ 0mm x-n zg onai wherein R is analiphatic group containing from 10 to 20 carbon atoms representing theresidue of a higher fatty acid; R1 is one of the group consisting ofhydrogen and lower alkyl radicals; R:

is one of the group consisting of alkylene and lower alkyl substitutedalkylene radicals; and X represents a hydroxyl radical.

'7. A soft, pliable textile material composed of or containingcellulosic fibers having intimately associated therewith and stronglyadsorbed therein a finishing agent composed of a compound of the groupconsisting of substances of the formula

